CN115991726A - Metal complexes, mixtures, compositions and organic electronic devices - Google Patents

Metal complexes, mixtures, compositions and organic electronic devices Download PDF

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CN115991726A
CN115991726A CN202111210513.1A CN202111210513A CN115991726A CN 115991726 A CN115991726 A CN 115991726A CN 202111210513 A CN202111210513 A CN 202111210513A CN 115991726 A CN115991726 A CN 115991726A
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梁志明
张静
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Guangzhou Chinaray Optoelectronic Materials Ltd
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Priority to CN202111210513.1A priority Critical patent/CN115991726A/en
Priority to DE112022002907.2T priority patent/DE112022002907T5/en
Priority to KR1020247010577A priority patent/KR20240052036A/en
Priority to PCT/CN2022/087005 priority patent/WO2023065614A1/en
Priority to EP22882239.1A priority patent/EP4421080A1/en
Publication of CN115991726A publication Critical patent/CN115991726A/en
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    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0033—Iridium compounds
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
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    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
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    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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Abstract

The present invention relates to an organometallic complex, a mixture, a composition, an organic electronic device, an electronic apparatus, and an application. The invention is thatThe metal complex provided contains at least one-CN, -F or-CF in its structure 3 And the electron withdrawing groups are substituted, and the electron withdrawing groups can help electron transmission in the device, so that electrons can be effectively used, the luminous efficiency of the device is improved, the starting voltage is reduced, and the service life of the device is prolonged. In addition, the LUMO energy level of the metal complex can be greatly stabilized by substituting an electron-withdrawing group, so that the luminescence is red-shifted, and the luminescence of the emitted red light can be more saturated; the conjugated system of the metal complex can be increased through the phenyl group limited in the heteroatom-containing system, so that the luminescence is red shifted; the two groups are used cooperatively, so that the luminescence of the metal complex can be greatly red-shifted, thereby realizing high-efficiency deep red light color.

Description

Metal complexes, mixtures, compositions and organic electronic devices
Technical Field
The invention belongs to the field of organic electroluminescence, and particularly relates to a metal complex, a mixture, a composition and an organic electronic device thereof.
Background
In flat panel displays and lighting applications, organic Light Emitting Diodes (OLEDs) have the advantages of low cost, light weight, low operating voltage, high brightness, color tunability, wide viewing angle, easy assembly, and low power consumption, and thus are the most promising display technologies.
In order to increase the luminous efficiency of organic light emitting diodes, various fluorescent and phosphorescent based luminescent material systems have been developed. The organic light emitting diode using the fluorescent material has high reliability, but the internal electroluminescent quantum efficiency thereof is limited to 25% under the excitation of an electric field. In contrast, since the branching ratio of the singlet excited state and the triplet excited state of excitons is 1:3, the organic light emitting diode using the phosphorescent material can achieve almost 100% internal light emission quantum efficiency. For small molecular organic matters, the spin orbit coupling can be improved by doping heavy metal centers to form metal complexes, intersystem crossing is easy to occur under the excitation of an electric field, and therefore triplet state excitation is effectively obtained.
Complexes based on iridium (III) are a class of materials widely used in high efficiency OLEDs, with higher efficiency and stability. Baldo et al report the use of fac-tris (2-phenylpyridine) iridium (III) [ Ir (ppy) 3 ]As a phosphorescent light-emitting material, 4'-N, N' -dicarbazole-biphenyl (CBP) is a high quantum efficiency OLED as a host material (appl. Phys. Lett.1999,75,4). Another example of a phosphorescent material is the sky blue complex bis [2- (4 ',6' -difluorophenyl) pyridine-N, C2]Iridium (III) picolinate (FIrpic), which when doped into a high triplet energy matrix, exhibits extremely high photoluminescence quantum efficiencies of about 60% in solution and almost 100% in solid films (appl. Phys. Lett.2001,79,2082). Although iridium (III) systems based on 2-phenylpyridine and its derivatives have been used in large numbers for the preparation of OLEDs, device performance,in particular, the life span still needs to be improved.
It is therefore desirable to develop such novel high performance metal complexes to further increase the lifetime of the device.
Disclosure of Invention
Based on this, there is a need to improve the stability of metal-organic complexes and the efficiency and lifetime of organic light emitting devices. Objects of the present invention include providing a metal complex and mixtures, compositions, organic electronic devices, electronic devices and applications thereof. The metal organic complex luminescent material has the advantages of simple synthesis, novel structure and good performance.
In a first aspect of the present invention, there is provided a metal complex having a structure represented by formula (I) or formula (II):
Figure BDA0003308665060000011
wherein,,
l is selected from monovalent anionic organic ligands;
m is selected from 1 or 2 or 3;
X 1 ，X 2 ，X 3 each occurrence is independently selected from CR 1 Or N;
X 4 ，X 5 ，X 6 ，X 7 ，X 8 ，X 9 each occurrence is independently selected from CR 2 Or N;
y is independently selected from CR for each occurrence 3 R 4 ，NR 3 O, S or SO 2 ；
R 1 ，R 2 ，R 3 ，R 4 Each occurrence is independently selected from: -H, -D, a linear alkyl group having 1 to 20C atoms, a linear alkoxy group having 1 to 20C atoms, a linear thioalkoxy group having 1 to 20C atoms, a branched alkyl group having 3 to 20C atoms, a cyclic alkyl group having 3 to 20C atoms, a branched alkoxy group having 3 to 20C atoms, or a cyclic alkoxy group having 3 to 20C atoms, a branched thioalkoxy group having 3 to 20C atoms, or a cyclic thio group having 3 to 20C atomsAlkoxy, silyl, keto having 1 to 20C atoms, alkoxycarbonyl having 2 to 20C atoms, aryloxycarbonyl having 7 to 20C atoms, -CN, carbamoyl, haloformyl, formyl, isocyano, isocyanato, thiocyanate, isothiocyanate, hydroxy, nitro, -CF 3 -Cl, -Br, -F, an aromatic group having 6 to 60 ring atoms substituted or unsubstituted, a heteroaromatic group having 5 to 60 ring atoms substituted or unsubstituted, an aryloxy group having 6 to 60 ring atoms substituted or unsubstituted, a heteroaryloxy group having 5 to 60 ring atoms substituted or unsubstituted, or a combination of these groups; adjacent R 1 Or adjacent R 2 With or without each other being cyclic;
at least one R 2 Selected from-CN, -F or-CF 3 。
In a second aspect of the invention, there is provided a mixture comprising the metal complex of the first aspect of the invention, the mixture further comprising an organic functional material. In some embodiments, the organic functional material is selected from at least one of a hole injecting material, a hole transporting material, an electron injecting material, an electron blocking material, a hole blocking material, a light emitting material, a host material, and an organic dye.
In a third aspect of the present invention there is provided a composition comprising a metal complex according to the first aspect of the present invention or a mixture according to the second aspect of the present invention, the composition further comprising at least one organic solvent.
In a fourth aspect of the invention, there is provided an organic electronic device comprising a metal complex according to the first aspect of the invention or a mixture according to the second aspect of the invention; or the organic electronic device is prepared from the composition according to the third aspect of the invention.
The technical scheme of the invention has at least the following beneficial effects:
the metal complex provided by the invention contains at least one-CN, -F or-CF 3 Electron withdrawing groups capable of facilitating electron transport in the device, thereby allowing electrons to passAnd the light-emitting layers are gathered, so that the light-emitting efficiency of the device is improved, the starting voltage is reduced, and the service life of the device is prolonged.
The metal complex provided by the invention can provide higher luminous efficiency and longer service life of the device when being used for OLED, especially used as a doping material of a luminous layer.
By CN, -F or-CF 3 The electron-withdrawing group is substituted, the LUMO energy level of the metal complex can be greatly stabilized, the luminescence is red-shifted, and the luminescence of the red light can be more saturated. The conjugated system of the metal complex can be increased by the phenyl group defined in the heteroatom-containing system, so that the luminescence can be red-shifted. The electron withdrawing group is used in combination with two groups of phenyl groups defined in the heteroatom-containing system, so that the luminescence of the metal complex can be greatly red-shifted, and the high-efficiency deep red light color is realized.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It should be understood that these embodiments and examples are provided solely for the purpose of illustrating the invention and are not intended to limit the scope of the invention in order that the present disclosure may be more thorough and complete. It will also be appreciated that the present invention may be embodied in many different forms and is not limited to the embodiments and examples described herein, but may be modified or altered by those skilled in the art without departing from the spirit of the invention, and equivalents thereof fall within the scope of the present application. Furthermore, in the following description, numerous specific details are set forth in order to provide a more thorough understanding of the invention, it being understood that the invention may be practiced without one or more of these details.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments and examples only and is not intended to be limiting of the invention.
The term "and/or," "and/or," as used herein, includes any one of two or more of the listed items in relation to each other, as well as any and all combinations of the listed items in relation to each other, including any two of the listed items in relation to each other, any more of the listed items in relation to each other, or all combinations of the listed items in relation to each other. It should be noted that, when at least three items are connected by a combination of at least two conjunctions selected from "and/or", "or/and", "and/or", it should be understood that, in this application, the technical solutions certainly include technical solutions that all use "logical and" connection, and also certainly include technical solutions that all use "logical or" connection. For example, "a and/or B" includes three parallel schemes A, B and a+b. For another example, the technical schemes of "a, and/or B, and/or C, and/or D" include any one of A, B, C, D (i.e., the technical scheme of "logical or" connection), and also include any and all combinations of A, B, C, D, i.e., any two or three of A, B, C, D, and also include four combinations of A, B, C, D (i.e., the technical scheme of "logical and" connection).
In the present invention, the composition and the printing ink, or ink, have the same meaning and are interchangeable.
In the present invention, the aryl, aromatic and aromatic ring systems have the same meaning and are interchangeable.
In the present invention, heteroaryl, heteroaromatic groups, heteroaromatic and heteroaromatic ring systems have the same meaning and are interchangeable.
In the present invention, the "heteroatom" is a non-carbon atom, and may be an N atom, an O atom, an S atom, or the like.
In the present invention, "substituted" means that a hydrogen atom in a substituted group is substituted by a substituent.
In the present invention, "substituted or unsubstituted" means that the defined group may or may not be substituted. When a defined group is substituted, it is understood that the defined group may be substituted with one or more substituents R selected from, but not limited to: deuterium, cyano, isocyano, nitro or halogen, alkyl containing 1 to 20C atoms, heterocyclyl containing 3 to 20 ring atoms, aromatic containing 6 to 20 ring atoms, heteroaromatic containing 5 to 20 ring atoms, -NR' R ", silane, carbonyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, haloformyl, formyl, isocyanate, thiocyanate, isothiocyanate, hydroxyl, trifluoromethyl, and which may be further substituted with substituents acceptable in the art; it is understood that R 'and R "in-NR' R" are each independently selected from, but not limited to: H. deuterium atoms, cyano groups, isocyano groups, nitro groups or halogen groups, alkyl groups containing 1 to 10C atoms, heterocyclic groups containing 3 to 20 ring atoms, aromatic groups containing 6 to 20 ring atoms, heteroaromatic groups containing 5 to 20 ring atoms. Preferably, R is selected from, but not limited to: deuterium atoms, cyano groups, isocyano groups, nitro groups or halogen groups, alkyl groups containing 1 to 10C atoms, heterocyclic groups containing 3 to 10 ring atoms, aromatic groups containing 6 to 20 ring atoms, heteroaromatic groups containing 5 to 20 ring atoms, silane groups, carbonyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, carbamoyl groups, haloformyl groups, formyl groups, isocyanate groups, thiocyanate groups, isothiocyanate groups, hydroxyl groups, trifluoromethyl groups, and which may be further substituted with substituents acceptable in the art.
In the present invention, hydroxyl means-OH, carboxyl means-COOH, carbonyl means-C (=O) -, and amino means-NH, unless otherwise specified 2 Formyl means-C (=o) H, haloformyl means-C (=o) Z (wherein Z represents halogen), carbamoyl means-C (=o) NH 2 Isocyanate groups refer to-NCO and isothiocyanate groups refer to-NCS.
In the present invention, the number of atoms described by a numerical range includes both the end points of the numerical range and also includes each integer of the two end points. For example, "C 1-10 Alkyl "means an alkyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms. "containing 3 to 10 ring atoms" means containing 3, 4, 5, 6, 7, 8, 9 or 10 ring atoms.
In the present invention, the "number of ring atoms" means the number of atoms among atoms constituting the ring itself of a structural compound (for example, a monocyclic compound, a condensed ring compound, a crosslinked compound, a carbocyclic compound, a heterocyclic compound) in which atoms are bonded to form a ring. When the ring is substituted with a substituent, the atoms contained in the substituent are not included in the ring-forming atoms. The same applies to the "number of ring atoms" described below, unless otherwise specified. For example, the number of ring atoms of the benzene ring is 6, the number of ring atoms of the naphthalene ring is 10, and the number of ring atoms of the thienyl group is 5. For another example, the number of ring atoms of methylbenzene is 6.
"aryl or aromatic group" refers to an aromatic hydrocarbon group derived from an aromatic ring compound by removal of one hydrogen atom, which may be a monocyclic aryl group, or a fused ring aryl group, or a polycyclic aryl group, at least one of which is an aromatic ring system for a polycyclic species. For example, "substituted or unsubstituted aryl group having 6 to 40 ring atoms" means an aryl group having 6 to 40 ring atoms, preferably a substituted or unsubstituted aryl group having 6 to 30 ring atoms, more preferably a substituted or unsubstituted aryl group having 6 to 18 ring atoms, particularly preferably a substituted or unsubstituted aryl group having 6 to 14 ring atoms, and the aryl group is optionally further substituted; suitable examples include, but are not limited to: phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, fluoranthryl, triphenylenyl, pyrenyl, perylenyl, tetracenyl, fluorenyl, perylenyl, acenaphthylenyl and derivatives thereof. It will be appreciated that a plurality of aryl groups may also be interrupted by short non-aromatic units (e.g. <10% of non-H atoms, such as C, N or O atoms), such as acenaphthene, fluorene, or 9, 9-diaryl fluorene, triarylamine, diaryl ether systems in particular should also be included in the definition of aryl groups.
"heteroaryl or heteroaromatic group" means that at least one carbon atom is replaced by a non-carbon atom on the basis of an aryl group, which may be an N atom, an O atom, an S atom, or the like. For example, "substituted or unsubstituted heteroaryl having 5 to 40 ring atoms" refers to heteroaryl having 5 to 40 ring atoms, preferably substituted or unsubstituted heteroaryl having 6 to 30 ring atoms, more preferably substituted or unsubstituted heteroaryl having 6 to 18 ring atoms, particularly preferably substituted or unsubstituted heteroaryl having 6 to 14 ring atoms, and the heteroaryl is optionally further substituted, suitable examples include, but are not limited to: thienyl, furyl, pyrrolyl, imidazolyl, diazolyl, triazolyl, imidazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, benzothienyl, benzofuranyl, indolyl, pyrroloimidazolyl, pyrrolopyrrolyl, thienopyrrolyl, furopyrrolyl, furofuranyl, thienofuranyl, benzisoxazolyl, benzisothiazolyl, benzimidazolyl, phthalazinyl, phenanthridinyl, primary pyridyl, quinazolinone, dibenzothienyl, dibenzofuranyl, carbazolyl, and derivatives thereof.
In the present invention, "alkyl" may denote a linear, branched and/or cyclic alkyl group. The carbon number of the alkyl group may be 1 to 50, 1 to 30, 1 to 20, 1 to 10, or 1 to 6. Non-limiting examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl, adamantyl, and the like.
In the present invention, the abbreviations of the substituents correspond to: n-n, sec-sec, i-iso, t-tert, o-o, m-m, p-pair, memethyl, et ethyl, pr propyl, bu butyl, am-n-pentyl, hx hexyl, cy cyclohexyl.
"halogen" or "halo" refers to F, cl, br or I.
The term "alkoxy" refers to a group of the structure "-O-alkyl", i.e. an alkyl group as defined above is attached to other groups via an oxygen atom. Phrases containing this term, suitable examples include, but are not limited to: methoxy (-O-CH) 3 or-OMe), ethoxy (-O-CH 2 CH 3 or-OEt) and t-butoxy (-O-C (CH) 3 ) 3 or-OtBu).
In the present invention, "×" indicates a ligation site.
In the present invention, when the same group contains a plurality of substituents of the same symbol, each substituent may be the same or different from each other, for example
Figure BDA0003308665060000031
6R on benzene ring 0 May be the same or different from each other.
In the present invention, a single bond to which a substituent is attached extends through the corresponding ring, meaning that the substituent may be attached to an optional position on the ring, e.g
Figure BDA0003308665060000041
R in (2) is connected with any substitutable site of benzene ring; for example->
Figure BDA0003308665060000042
Representation->
Figure BDA0003308665060000043
Can be combined with
Figure BDA0003308665060000044
Optionally forming a fused ring at an optional position on the benzene ring.
The cyclic alkyl or cycloalkyl groups according to the invention have the same meaning and are interchangeable.
In the present invention, "adjacent group" means that there is no substitutable site between two substituents.
As used in this disclosure, "a combination thereof," "any combination thereof," and the like include all suitable combinations of any two or more of the listed items.
In the present invention, "further", "still further", "particularly" and the like are used for descriptive purposes to indicate differences in content but should not be construed as limiting the scope of the invention.
In the present invention, "optional" means optional or not, that is, means any one selected from two parallel schemes of "with" or "without". If multiple "alternatives" occur in a technical solution, if no particular description exists and there is no contradiction or mutual constraint, then each "alternative" is independent.
In the invention, the technical characteristics described in an open mode comprise a closed technical scheme composed of the listed characteristics and also comprise an open technical scheme comprising the listed characteristics.
The invention relates to a metal complex, the structure of which is shown as a formula (I) or a formula (II):
Figure BDA0003308665060000045
wherein L is selected from monovalent anionic organic ligands; m is selected from 1 or 2 or 3;
X 1 ，X 2 ，X 3 each occurrence is independently selected from CR 1 Or N;
X 4 ，X 5 ，X 6 ，X 7 ，X 8 ，X 9 each occurrence is independently selected from CR 2 Or N;
y is independently selected from CR for each occurrence 3 R 4 ，NR 3 O, S or SO 2 ；
R 1 ，R 2 ，R 3 ，R 4 Each occurrence is independently selected from: -H, -D, linear alkyl having 1 to 20C atoms, linear alkoxy having 1 to 20C atoms, linear thioalkoxy having 1 to 20C atoms, branched alkyl having 3 to 20C atoms, or cyclic alkyl having 3 to 20C atoms, branched alkoxy having 3 to 20C atoms, cyclic alkoxy having 3 to 20C atoms, branched thioalkoxy having 3 to 20C atoms, or cyclic thioalkoxy having 3 to 20C atoms, silyl, keto having 1 to 20C atoms, alkoxycarbonyl having 2 to 20C atoms, aryloxycarbonyl having 7 to 20C atoms, -CN, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, -CF 3 -Cl, -Br, -F, substitutionOr an unsubstituted aryl group having from 6 to 60 ring atoms, a substituted or unsubstituted heteroaryl group having from 5 to 60 ring atoms, a substituted or unsubstituted aryloxy group having from 6 to 60 ring atoms, a substituted or unsubstituted heteroaryloxy group having from 5 to 60 ring atoms, or a combination of these groups; adjacent R 1 Or adjacent R 2 With or without each other being cyclic;
at least one R 2 Selected from-CN, -F or-CF 3 。
In some embodiments, the metal complex is selected from compounds of any of formulas (1-1) to (1-6):
Figure BDA0003308665060000046
Figure BDA0003308665060000051
in some embodiments, R 1 Selected from the group consisting of-H, -D, -CN, nitro, -CF 3 -Cl, -Br, -F, -I, a linear alkyl group having 1 to 10C atoms, a branched or cyclic alkyl group having 3 to 10C atoms, substituted by R * Substituted or unsubstituted aromatic radical having 6 to 10C atoms, substituted by R * A substituted or unsubstituted heteroaromatic group having 5 to 13 ring atoms; wherein: r is R * Selected from-D, -CN, nitro, -CF 3 -Cl, -Br, -F, -I, a linear alkyl group having 1 to 10C atoms, or a branched or cyclic alkyl group having 3 to 10C atoms, or a phenyl group, or a biphenyl group, or a naphthyl group.
In one embodiment, adjacent R 1 Forming a 6-membered ring with each other; examples are the structures shown in the following (A-37).
In some preferred embodiments, R 1 Selected from any one of the following groups: -H, -CH 3 Tertiary butyl, phenyl, pyridyl and pyrazinyl.
In some embodiments, R 2 Selected from the group consisting of-H, -D, -CN, nitro, -CF 3 -Cl, -Br, -F, -I, with 1 to 10C atomsStraight chain alkyl of the sub, branched or cyclic alkyl having 3 to 10C atoms, substituted by R * Substituted or unsubstituted aromatic radical having 6 to 10C atoms, substituted by R * A substituted or unsubstituted heteroaromatic group having 5 to 13 ring atoms; wherein: r is R * Selected from-D, -CN, nitro, -CF 3 -Cl, -Br, -F, -I, a linear alkyl group having 1 to 10C atoms, or a branched or cyclic alkyl group having 3 to 10C atoms, or a phenyl group, or a biphenyl group, or a naphthyl group.
In some preferred embodiments, R 2 Selected from any one of the following groups: -H, -D, -CH 3 Isopropyl, -F, -CF 3 and-CN.
In some embodiments, X 7 Selected from CR 2 And R is 2 Selected from-CN, -F or-CF 3 。
In some embodiments, R 3 、R 4 Independently selected from-H, -D, straight chain alkyl having 1 to 10C atoms, branched or cyclic alkyl having 3 to 10C atoms, and R * Substituted or unsubstituted aromatic radical having 6 to 10C atoms, substituted by R * A substituted or unsubstituted heteroaromatic group having 5 to 13 ring atoms; r is R * Selected from-D, -CN, nitro, -CF 3 -Cl, -Br, -F, -I, a linear alkyl group having 1 to 10C atoms, or a branched or cyclic alkyl group having 3 to 10C atoms, or a phenyl group, or a biphenyl group, or a naphthyl group.
In some preferred embodiments, R 3 、R 4 Each independently selected from any one of the following groups: -H, -CH 3 Isopropyl, tert-butyl and phenyl.
In some embodiments, a compound of formula (I)
Figure BDA0003308665060000052
A group selected from any one of the following:
Figure BDA0003308665060000053
wherein: * Representing the ligation site.
In some embodiments, in formula (II)
Figure BDA0003308665060000061
A group selected from any one of the following:
Figure BDA0003308665060000062
in some embodiments, a compound of formula (I), formula (II)
Figure BDA0003308665060000063
Each independently selected from any one of the following groups:
Figure BDA0003308665060000064
/>
Figure BDA0003308665060000071
in some embodiments, a compound of formula (I)
Figure BDA0003308665060000072
Any one structure selected from (A-1) to (A-48):
Figure BDA0003308665060000073
/>
Figure BDA0003308665060000081
wherein, represents the site of attachment to Ir; (a-1) to (a-48) may be further substituted with R.
In some embodiments, a compound of formula (I)
Figure BDA0003308665060000082
Any one structure selected from (B-1) to (B-24):
Figure BDA0003308665060000083
/>
Figure BDA0003308665060000091
wherein, represents the site of attachment to Ir; (B-1) to (B-24) may be further substituted by R.
In some embodiments, a compound of formula (I)
Figure BDA0003308665060000092
Any one structure selected from (C-1) to (C-36):
Figure BDA0003308665060000093
/>
Figure BDA0003308665060000101
Wherein, represents the site of attachment to Ir; (C-1) to (C-36) may be further substituted by R.
In some embodiments, in formula (II)
Figure BDA0003308665060000102
Any one structure selected from (D-1) to (D-35):
Figure BDA0003308665060000103
/>
wherein, represents the site of attachment to Ir; (D-1) to (D-35) may be further substituted with R.
In some embodiments, in formula (II)
Figure BDA0003308665060000111
Any one structure selected from (E-1) to (E-31):
Figure BDA0003308665060000112
wherein, represents the site of attachment to Ir; (E-1) to (E-31) may be further substituted with R.
In some embodiments, in formula (II)
Figure BDA0003308665060000113
Any one structure selected from (F-1) to (F-24):
Figure BDA0003308665060000121
wherein, represents the site of attachment to Ir; (F-1) to (F-24) may be further substituted by R.
In some embodiments, L is a monovalent bidentate anionic ligand,
further, L is selected from the following structural formulas:
Figure BDA0003308665060000122
wherein,,
Ar 1 、Ar 2 、Ar 3 independently selected from a substituted or unsubstituted aromatic group having 5 to 30 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms, or a substituted or unsubstituted non-aromatic ring system having 5 to 30 ring atoms;
R 5 、R 6 、R 7 each occurrence is independently selected from: -H, -D, a linear alkyl group having 1 to 20C atoms, a linear alkoxy group having 1 to 20C atoms, a linear thioalkoxy group having 1 to 20C atoms, a branched alkyl group having 3 to 20C atoms, a cyclic alkyl group having 3 to 20C atoms, a branched alkoxy group having 3 to 20C atoms, a cyclic alkoxy group having 3 to 20C atoms, a branched thioalkoxy group having 3 to 20C atoms, a cyclic ring having 3 to 20C atoms Thioalkoxy, silyl, keto having 1 to 20C atoms, alkoxycarbonyl having 2 to 20C atoms, aryloxycarbonyl having 7 to 20C atoms, -CN, carbamoyl, haloformyl, formyl, isocyano, thiocyanate, isothiocyanate, hydroxy, nitro, -CF 3 -Cl, -Br, -F, an aromatic group having 6 to 60 ring atoms substituted or unsubstituted, a heteroaromatic group having 5 to 60 ring atoms substituted or unsubstituted, an aryloxy group having 6 to 60 ring atoms substituted or unsubstituted, a heteroaryloxy group having 5 to 60 ring atoms substituted or unsubstituted, or a combination of the foregoing; * Represents the site of attachment to Ir.
In some embodiments, R 5 、R 6 、R 7 Each occurrence is independently selected from: -H, -D, a linear alkyl group having 1 to 10C atoms, a branched alkyl group having 3 to 10C atoms, or a cyclic alkyl group having 3 to 10C atoms, or phenyl, or biphenyl, or naphthyl, or pyrimidinyl, or pyridinyl, or a combination of the foregoing.
In some embodiments, R 6 is-H.
In some embodiments, R 5 、R 7 Selected from the same groups.
In some embodiments, R 5 、R 7 Each occurrence is independently selected from: methyl, ethyl, tert-butyl, phenyl or adamantyl or cyclohexyl.
In some embodiments, ar 1 、Ar 2 、Ar 3 Each independently selected from the following groups:
Figure BDA0003308665060000131
wherein,,
v is independently selected from C, CR for each occurrence 8 Or N; any two V may be the same or different;
w is independently selected from CR for each occurrence 9 R 10 、NR 9 、O、S、N、PR 9 、BR 9 Or SiR 9 R 10 The method comprises the steps of carrying out a first treatment on the surface of the When the number of W is 2 or more, any two W may be the same or different;
R 8 、R 9 、R 10 each occurrence is independently selected from: -H, -D, linear alkyl having 1 to 20C atoms, linear alkoxy having 1 to 20C atoms, linear thioalkoxy having 1 to 20C atoms, branched alkyl having 3 to 20C atoms, or cyclic alkyl having 3 to 20C atoms, branched alkoxy having 3 to 20C atoms, or cyclic alkoxy having 3 to 20C atoms, branched thioalkoxy having 3 to 20C atoms, or cyclic thioalkoxy having 3 to 20C atoms, silyl, keto having 1 to 20C atoms, alkoxycarbonyl having 2 to 20C atoms, aryloxycarbonyl having 7 to 20C atoms, -CN, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, -CF 3 -Cl, -Br, -F, a substituted or unsubstituted alkenyl group having from 2 to 20C atoms, a substituted or unsubstituted aryl group having from 6 to 60 ring atoms, a substituted or unsubstituted heteroaryl group having from 5 to 60 ring atoms, a substituted or unsubstituted aryloxy group having from 6 to 60 ring atoms, a substituted or unsubstituted heteroaryloxy group having from 5 to 60 ring atoms, or a suitable combination of the foregoing; adjacent R 8 And/or R 9 With or without each other.
In one embodiment, adjacent R 8 Forming a 6-membered ring with each other; see structures (H-8), (H-25), (H-27), (H-28), (H-42) and the like below.
In some embodiments, R 8 、R 9 、R 10 Each occurrence is independently selected from any one of the following groups: -H, -D, straight chain alkyl having 1 to 10C atoms, branched alkyl having 3 to 10C atoms, cyclic alkyl having 3 to 10C atoms, -CN, nitro, -CF 3 -Cl, -Br, -F, -I, phenyl, biphenyl, naphthyl, and the like.
In some embodiments, V is independently selected from C, CH, C (CH) 3 ) Or N.
In some embodiments, each W is independently O, S, C (CH 3 ) 2 、CH 2 Or NH or N-Ph.
In some preferred embodiments, L is preferably any one of structures (G-1) to (G-28):
Figure BDA0003308665060000132
Figure BDA0003308665060000141
Therein, V, W, R 5 、R 7 、R 8 Is defined as above;
wherein one Q in the ligand is selected from C, and the other Q is selected from N.
Wherein (G-13) is two R 8 Cyclizing, (G-19) is R 8 And R is 9 Forming a ring.
Preferably, L is selected from any one of (G-1) to (G-6), (G-16) to (G-18), (G-21), (G-25), (G-26); more preferably, L is selected from (G-1) or (G-25) or (G-26).
In some embodiments, L is selected from any one of structures (H-1) to (H-42):
Figure BDA0003308665060000142
wherein (H-1) to (H-42) may be further substituted by R.
Wherein (H-8) is two R 8 The ring is formed by a carbon-carbon double bond.
In some embodiments, the metal complex is selected from any one of formulas (2-1) to (2-16):
Figure BDA0003308665060000151
preferably, X in the formulae (2-1) to (2-15) 7 Selected from CR 2 And R is 2 Selected from-CN, -F or-CF 3 。
The specific structure of the metal complex according to the present invention is given below as being suitable, but not limited thereto.
In some specific embodiments, the metal complex structures are shown in tables 1 and 2 below.
In tables 1 and 2, L1 represents
Figure BDA0003308665060000161
L2 represents->
Figure BDA0003308665060000162
TABLE 1 structural examples of the Compounds of formula (I)
Figure BDA0003308665060000163
/>
Figure BDA0003308665060000171
/>
Figure BDA0003308665060000181
TABLE 2 structural examples of the compounds of formula (II)
Figure BDA0003308665060000182
/>
Figure BDA0003308665060000191
The metal complex can be used as a functional material in electronic devices. Organic functional materials include, but are not limited to: a Hole Injection Material (HIM), a Hole Transport Material (HTM), an Electron Transport Material (ETM), an Electron Injection Material (EIM), an Electron Blocking Material (EBM), a Hole Blocking Material (HBM), a light emitting body (Emitter), a Host material (Host), and the like.
In one embodiment, the metal complex is a luminescent material having a luminescent wavelength between 300nm and 1000 nm; further, the metal complex has an emission wavelength between 350nm and 900 nm; still further, the metal complex has a luminescence wavelength between 400nm and 800 nm. Here, the light emission means photoluminescence or electroluminescence.
In some embodiments, the metal complex has an electroluminescent efficiency of ≡30%; further, the electroluminescent efficiency of the metal complex is more than or equal to 40%; furthermore, the electroluminescent efficiency of the metal complex is more than or equal to 50%; in particular, the electroluminescent efficiency of the metal complex is more than or equal to 60 percent.
In some embodiments, the metal complex is used in the light emitting layer as a phosphorescent guest. The phosphorescent guest material must have an appropriate triplet energy level (T 1 ). In some embodiments, T of the metal complex 1 Not less than 2.0eV; further, T of the metal complex 1 Not less than 2.2eV; further, T of the metal complex 1 Not less than 2.4eV; in particular, T of the metal complex 1 ≥2.6eV。
As a functional material, good thermal stability is desired. In some embodiments, the metal complex has a glass transition temperature Tg of greater than or equal to 100 ℃. In some embodiments, the metal complex has a glass transition temperature Tg of greater than or equal to 120 ℃. In some embodiments, the metal complex has a glass transition temperature Tg of greater than or equal to 160 ℃. In some embodiments, the metal complex has a glass transition temperature Tg of 180 ℃.
In a further aspect the invention provides a mixture comprising a metal complex as described above and at least one organic functional material.
The organic functional material may be selected from a Hole Injection Material (HIM), a Hole Transport Material (HTM), an Electron Transport Material (ETM), an Electron Injection Material (EIM), an Electron Blocking Material (EBM), a Hole Blocking Material (HBM), a light emitting material (Emitter), a Host material (Host), and an organic dye. Various organic functional materials are described in detail in WO2010135519A1, US20090134784A1 and WO2011110277A1, the entire contents of these 3 patent documents being hereby incorporated by reference.
In some embodiments, the mass content of the metal complex in the mixture is 0.01wt% to 30wt%; in a further embodiment, the mass content of the metal complex is 0.5wt% to 20wt%; in a further embodiment, the mass content of the metal complex is 2wt% to 15wt%; in some particular embodiments, the metal complex is present in an amount of 5wt% to 15wt%.
In an embodiment, in the mixture, the another organic functional material is selected from a host material; in one embodiment, the mixture comprises one metal complex as described above and two different host materials.
The invention further relates to a composition comprising a metal complex or mixture as described above and at least one organic solvent (denoted as first solvent).
In some embodiments, the organic solvent is selected from any one of aromatic, heteroaromatic, ester, aromatic ketone, aromatic ether, aliphatic ketone, aliphatic ether, alicyclic, olefinic, borate, and phosphate compounds, or a mixture of any two or more of the foregoing solvents.
In some embodiments, the organic solvent comprises an aromatic or heteroaromatic based solvent.
In some embodiments, examples of aromatic or heteroaromatic-based solvents suitable for the present invention include, but are not limited to: p-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1, 4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, dipentylbenzene, tripentylbenzene, pentyltoluenes, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,2,3, 4-tetramethylbenzene, 1,2,3, 5-tetramethylbenzene, 1,2,4, 5-tetramethylbenzene, butylbenzene, dodecylbenzene, dihexylbenzene, dibutylbenzene, p-diisopropylbenzene, cyclohexylbenzene, benzylbutylbenzene, dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, 1-methylnaphthalene, 1,2, 4-trichlorobenzene, 4-difluorodiphenyl methane, 1, 2-dimethoxy-4- (1-propenyl) benzene, diphenyl methane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, α -dichlorodiphenyl methane, 4- (3-phenylpropyl) pyridine, benzyl benzoate, 1-bis (3, 4-dimethylphenyl) ethane, 2-isopropylnaphthalene, 2-quinolinecarboxylic acid, ethyl ester, 2-methylfuran, etc.
In some embodiments, examples of aromatic ketone-based solvents suitable for the present invention include, but are not limited to: 1-tetralone, 2- (phenylepoxy) tetralone, 6- (methoxy) tetralone, acetophenone, propiophenone, benzophenone, and derivatives thereof, such as 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-methylpropionophenone, 3-methylpropionophenone, 2-methylpropionophenone, and the like.
In some embodiments, examples of aromatic ether-based solvents suitable for the present invention include, but are not limited to: 3-phenoxytoluene, butoxybenzene, p-anisaldehyde dimethyl acetal, tetrahydro-2-phenoxy-2H-pyran, 1, 2-dimethoxy-4- (1-propenyl) benzene, 1, 4-benzodioxane, 1, 3-dipropylbenzene, 2, 5-dimethoxytoluene, 4-ethylben-ther, 1, 3-dipropoxybenzene, 1,2, 4-trimethoxybenzene, 4- (1-propenyl) -1, 2-dimethoxybenzene, 1, 3-dimethoxybenzene, glycidyl phenyl ether, dibenzyl ether, 4-t-butyl anisole, trans-p-propenyl anisole, 1, 2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2-phenoxymethyl ether, 2-phenoxytetrahydrofuran, ethyl-2-naphthyl ether, and the like.
In some embodiments, examples of aliphatic ketone-based solvents suitable for the present invention include, but are not limited to: 2-nonene, 3-nonene, 5-nonene, 2-decanone, 2, 5-adipone, 2,6, 8-trimethyl-4-nonene, fenchyl ketone, phorone, isophorone, di-n-amyl ketone, and the like; or aliphatic ethers such as amyl ether, hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and the like.
In some embodiments, examples of ester-based solvents suitable for the present invention include, but are not limited to: alkyl octanoates, alkyl sebacates, alkyl stearates, alkyl benzoates, alkyl phenylacetates, alkyl cinnamates, alkyl oxalates, alkyl maleates, alkyl lactones, alkyl oleates, and the like. Particular preference is given to octyl octanoate, diethyl sebacate, diallyl phthalate, isononyl isononanoate and the like.
The above-mentioned organic solvents may be used alone or as a mixture of two or more organic solvents.
In some embodiments, the composition may further comprise another organic solvent (which may be referred to as a second organic solvent). Examples of the other organic solvent (second organic solvent) include, but are not limited to: methanol, ethanol, 2-methoxyethanol, methylene chloride, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1,4 dioxane, acetone, methyl ethyl ketone, 1,2 dichloroethane, 3-phenoxytoluene, 1-trichloroethane, 1, 2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethylsulfoxide, tetrahydronaphthalene, decalin, indene, and the like, or any suitable mixtures of the foregoing solvents.
In some embodiments, a solvent particularly suitable for the present invention is a solvent having Hansen (Hansen) solubility parameters within the following ranges:
δ d (dispersion force) of 17.0-23.2 MPa 1/2 In particular in the range from 18.5 to 21.0MPa 1/2 Is defined by the range of (2); and/or
δ p (polar force) is 0.2-12.5 MPa 1/2 In particular in the range of 2.0 to 6.0MPa 1/2 Is defined by the range of (2); and/or
δ h The (hydrogen bond force) is between 0.9 and 14.2MPa 1/2 In particular in the range of 2.0 to 6.0MPa 1/2 Is not limited in terms of the range of (a).
In the composition of the invention, the organic solvent is selected taking into account its boiling point parameters. In the preparation of organic electronic devices, a composition containing an organic solvent is ejected from an inkjet printhead, attached to a substrate, and the organic solvent is subsequently evaporated to form a thin film comprising the metal complex of the present invention. The choice of an organic solvent with a suitable boiling point therefore prevents clogging of the nozzles of the inkjet print head.
In some embodiments, the organic solvent has a boiling point of ∈150 ℃; further, the boiling point of the organic solvent is more than or equal to 180 ℃; further, the boiling point of the organic solvent is more than or equal to 200 ℃; still further, the boiling point of the organic solvent is more than or equal to 250 ℃; in particular, the organic solvent has a boiling point of 275℃or more or 300℃or more. Boiling points in these ranges are beneficial in preventing nozzle clogging of inkjet printheads. The organic solvent may be evaporated from the solvent groups to form a film comprising the functional material.
In one embodiment, the composition according to the invention is a solution.
In another embodiment, the composition according to the invention is a suspension.
In some embodiments, the composition provided by the third aspect of the present invention comprises the metal complex of the first aspect of the present invention or the mixture of the second aspect of the present invention, the mass content of the metal complex or the mixture in the composition being 0.01wt% to 10wt%, further 0.1wt% to 5wt%, still further 0.2wt% to 5wt%, in particular 0.25wt% to 3wt%.
The invention also relates to the use of said composition as a coating or printing ink for the production of organic electronic devices, in particular by a printing or coating process.
Suitable printing or coating techniques include, but are not limited to, ink jet printing, letterpress printing, screen printing, dip coating, spin coating, doctor blade coating, roller printing, twist roller printing, lithographic printing, flexography, rotary printing, spray coating, brush coating, pad printing, slot die coating, or the like. Gravure printing, inkjet printing and inkjet printing are preferred. The solution or suspension may additionally include one or more components (e.g., surface active compounds, lubricants, wetting agents, dispersants, hydrophobing agents, binders, etc.) for adjusting viscosity, film forming properties, improving adhesion, etc.
The invention also provides the use of a metal complex, mixture or composition as described above in an organic electronic device.
The invention also provides an organic electronic device containing the metal complex or the mixture or prepared from the composition.
Further, an organic electronic device comprising a functional layer comprising the metal complex, mixture or prepared from the composition described above.
Wherein the organic electronic device may be selected from, but not limited to, organic Light Emitting Diodes (OLEDs), organic photovoltaic cells (OPVs), organic light emitting cells (olecs), organic Field Effect Transistors (OFETs), organic light emitting field effect transistors, organic lasers, organic spintronics devices, organic sensors, and organic plasmon emitting diodes (Organic Plasmon Emitting Diode), etc. In some embodiments, the organic electronic device is selected from the group consisting of organic electroluminescent devices, such as OLEDs, oleccs, organic light emitting field effect transistors, and the like. In some preferred embodiments, the organic electronic device is an OLED.
In some embodiments, the organic electronic device is an organic electroluminescent device comprising at least a cathode, an anode, and a light emitting layer; the light-emitting layer contains the metal complex, the mixture or is prepared from the composition.
Further, the organic electroluminescent device further comprises one or more other functional layers selected from a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Electron Blocking Layer (EBL), an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), a Hole Blocking Layer (HBL). Materials suitable for use in these functional layers are described in detail above and in WO2010135519A1, US20090134784A1 and WO2011110277A1, the entire contents of which 3 patent documents are hereby incorporated by reference.
In the light emitting device described above, in particular an OLED, it comprises a substrate, an anode, at least one light emitting layer and a cathode.
In the present invention, the substrate may be opaque or transparent, and a transparent substrate may be used to fabricate a transparent light emitting device; see, for example, bulovic et al Nature 1996,380, p29, and Gu et al, appl. Phys. Lett.1996,68, p2606. The substrate may be rigid or elastic. The substrate may be plastic, metal, semiconductor chip or glass. In particular embodiments, the substrate has a smooth surface. In the present invention, a substrate free of surface defects is a particularly desirable choice.
In some embodiments, the substrate is flexible and may be selected from a polymer film or plastic, preferably having a glass transition temperature Tg of 150 ℃ or higher; further, tg exceeds 200 ℃; still further, tg exceeds 250 ℃; in particular, tg exceeds 300 ℃. Examples of suitable flexible substrates include, but are not limited to: poly (ethylene terephthalate) (PET) and polyethylene glycol (2, 6-naphthalene) (PEN), and the like.
In the present invention, the anode may include a conductive metal, a metal oxide, or a conductive polymer. The anode can easily inject holes into a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), or a light emitting layer.
In some embodiments, the absolute value of the difference in HOMO or valence band energy levels of the anode's work function and the emitter in the light emitting layer or the p-type semiconductor material as a HIL or HTL or Electron Blocking Layer (EBL) is less than 0.5eV; further, the absolute value is less than 0.3eV; in particular, the absolute value is less than 0.2eV.
In some embodiments, examples of anode materials include, but are not limited to: al, cu, au, ag, mg, fe, co, ni, mn, pd, pt, ITO aluminum doped zinc oxide (AZO), and the like. Other anode materials are known and can be readily selected for use by one of ordinary skill in the art. The anode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.
In some embodiments, the anode is patterned. Patterned ITO conductive substrates are commercially available and can be used to prepare organic electronic devices according to the present invention.
In the present invention, the cathode may include a conductive metal or metal oxide. The cathode can easily inject electrons into the EIL or ETL or directly into the light emitting layer.
In some embodiments, the absolute value of the difference in LUMO or conduction band energy levels of the n-type semiconductor material of the light emitter in the work function and light emitting layer of the cathode or as an Electron Injection Layer (EIL) or Electron Transport Layer (ETL) or Hole Blocking Layer (HBL) is less than 0.5eV; further, the absolute value is less than 0.3eV; in particular, the absolute value is less than 0.2eV.
In principle, all materials which can be used as cathode of an OLED are possible as cathode materials for the device according to the invention. Examples of cathode materials include, but are not limited to: al, au, ag, ca, ba, mg, liF/Al, mgAg alloy and BaF 2 /Al, cu, fe, co, ni, mn, pd, pt, ITO, etc. The cathode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.
The invention also relates to the use of the electroluminescent device according to the invention in various electronic devices, including, but not limited to, display devices, lighting devices, light sources, sensors, etc.
The invention will be described in connection with the following examples, but it is not limited thereto, and it is to be understood that the appended claims summarize the scope of the invention and that certain changes made to the various embodiments of the invention which are contemplated by one skilled in the art are to be covered by the spirit and scope of the appended claims.
Wherein eq represents molar equivalent. The% by mass (w/w) is represented by mass.
1.1. Transition metal complex structure and synthetic route
Synthesis example 1: organometallic complex (5)
Figure BDA0003308665060000221
2.1. Synthetic intermediate (5-a):
in a dry two-necked flask was placed phenylboronic acid (1 eq), 3-chloro-6-bromodibenzofuran (1 eq,200 g), pd (PPh 3 ) 4 (0.05 eq, tetrakis (triphenylphosphine) palladium) and potassium carbonate (4 eq) were added, then 250mL of a mixed solution of dioxane and water in a volume ratio of 3:1 was added, the mixture was stirred at 90 ℃ for reaction for 12 hours, cooled to room temperature, dried by spin-drying after completion of the reaction, dried over dichloromethane and water solution, dried over magnesium sulfate and then dried by spin-drying again, and then separated and purified by a silica gel column to obtain a solid intermediate (5-a), 138.6g, yield 70%, and eimass spectrum showed a charge peak m/z= 278.51.
2.2. Synthetic intermediate (5-b):
in a dry two-necked flask was placed pinacol biborate (1.5 eq), intermediate (5-a) (1 eq,135 g), pd (dppf) 2 Cl 2 (0.05 eq) and potassium acetate (4 eq), then 250mL of a mixed solution of dioxane and water in a volume ratio of 3:1 was added, the mixture was stirred at 90 ℃ for reaction for 12 hours, cooled to room temperature, dried by spinning after the reaction was completed, dried by using methylene chloride and a water solution, dried by using magnesium sulfate, dried by spinning again, and then separated and purified by using a silica gel chromatographic column. To give solid intermediate (5-b), 145.7g, yield 81%, EI mass spectrum showing charge peaks m/z= 370.17.
2.3. Synthetic intermediate (5-c):
referring to the synthesis method of compound intermediate (5-a), the difference is that phenylboronic acid is changed to intermediate (5-b) (1 eq,140 g), and 3-chloro-6-bromodibenzofuran is changed to 1-chloroisoquinoline-6-carbonitrile. To give solid intermediate (5-c), 101.9g, yield 68%, EI mass spectrum showed charge peak m/z= 396.13.
2.4. Synthetic intermediate (5-d):
in a dry 250mL bottle were placed 7, 8-benzoquinoline (4.4 eq,50 g) and iridium trichloride trihydrate (2 eq), and the vacuum and filling with nitrogen were repeated three times, followed by the addition of ethylene glycol ethyl ether in a volume ratio of 3:1: a mixed solution of water (120 mL) was then stirred at 110deg.C for 24 hours, water (1000 mL) was added and the solid was filtered to give a reddish brown intermediate (5-d), 25.1g, 34% yield, EI mass spectrum showing charge peaks m/z= 1163.13.
2.5. Synthesizing the organometallic complex (5).
In a dry 250mL bottle, the intermediate (5-d) (1 eq,20 g) was placed, dissolved in a mixed solution of 300mL of methylene chloride and 100mL of methanol, then silver triflate (3 eq) was added, after reacting at room temperature for 12 hours, the solid was filtered off, and the filtrate was dried in vacuo, then a red solid was obtained. The red solid was placed in a dry 250mL bottle, intermediate (5-c) (1 eq) and sodium carbonate (5 eq) were added, diethyl ether (60 mL) and water (20 mL) were added as solvents, after blowing nitrogen, heated to 60 ℃ for reaction for 6 hours, a large amount of water (1000 mL) was added, the precipitated red solid was filtered, washed with water and methanol, dried, and separated and purified by a silica gel chromatography column, after recrystallization, a dark red solid metal complex (5) was obtained, 8.1g, yield 25%, and EI mass spectrum showed charge peak m/z= 944.21.
EXAMPLE 3 Synthesis of organometallic Complex (7)
Figure BDA0003308665060000231
3.1. Synthetic intermediate (7-a):
the reference compound intermediate (5-d) was synthesized with the difference that 7, 8-benzoquinoline was changed to intermediate (5-c) (4.4 eq,50 g). A reddish brown intermediate (7-a), 17.5g, yield 30%, was obtained, and EI mass spectrum showed charge peak m/z= 2036.34.
3.2. Synthesis of organometallic Complex (7)
In a dry 250mL bottle, the intermediate (7-a) (1 eq,15 g) was placed, sodium carbonate (5 eq) and acetylacetone (3 eq) were added to dissolve, after reacting for 24 hours at room temperature with a mixed solution of 300mL dichloromethane and 100mL methanol, the solution was evaporated in vacuo, extracted with water and dichloromethane, the organic layer was taken, then the solution was evaporated in vacuo to give a red solid, which was dried and purified by separation with a silica gel column, after recrystallization, a dark red solid metal complex (7) was obtained, 7.3g, yield 46%, and EI mass spectrum showed charge peak m/z= 1082.24.
EXAMPLE 4 Synthesis of organometallic Complex (17)
Figure BDA0003308665060000232
4.1. Synthetic intermediate (17-a):
the synthesis method of the reference compound intermediate (5-a) is different in that 3-chloro-6-bromodibenzofuran is changed into 3-chloro-6-bromodibenzothiophene (1 eq,200 g). Solid intermediate (17-a), 109.3g, was obtained in 55% yield, and EI mass spectrum showed charge peak m/z= 294.03.
4.2. Synthetic intermediate (17-b):
the synthesis method of the reference compound intermediate (5-b) is different in that the intermediate (5-a) is changed to the intermediate (17-a) (1 eq,100 g). Solid intermediate (17-b), 94.8g, yield 72%, EI mass spectrum showing charge peaks m/z= 386.15, was obtained.
4.3. Synthetic intermediate (17-c):
referring to the synthesis method of compound intermediate (5-a), the difference is that phenylboronic acid is changed to intermediate (17-b) (1 eq,100 g), and 3-chloro-6-bromodibenzofuran is changed to 1-chloroisoquinoline-6-carbonitrile. To give solid intermediate (17-c), 64.9g, yield 58%, EI mass spectrum showing charge peaks m/z= 412.10.
4.4. Synthetic intermediate (17-d):
the reference compound intermediate (5-d) was synthesized with the difference that 7, 8-benzoquinoline was changed to intermediate (17-c) (4.4 eq,60 g). A reddish brown intermediate (17-d), 19.5g, yield 28%, was obtained and the EI mass spectrum showed a charge peak m/z= 2100.25.
4.5. Synthesis of organometallic complex (17):
referring to the synthesis method of the metal complex (5), the difference is that the intermediate (5-d) is changed to the intermediate (17-d) (1 eq,18 g), and the intermediate (5-c) is changed to 2-phenylpyridine. This gave a dark red metal complex (17), 10g, yield 50%, and EI mass spectrum showed a charge peak m/z= 1169.22.
EXAMPLE 5 Synthesis of organometallic Complex (54)
Figure BDA0003308665060000241
5.1. Synthetic intermediate (54-a):
referring to the synthesis of compound intermediate (5-a), the difference is that phenylboronic acid is changed to intermediate (17-b) (1 eq,100 g), and 3-chloro-6-bromodibenzofuran is changed to 4-bromo-7-trifluoromethylquinazoline. This gave solid intermediate (54-a), 55.5g, yield 47%, EI mass spectrum showing charge peak m/z=456.09.
5.2. Synthetic intermediate (54-b):
referring to the synthesis of compound intermediate (5-d), the difference was that 7, 8-benzoquinoline was changed to intermediate (54-a) (4.4 eq,50 g). This gave a reddish brown intermediate (54-b), 14.7g, 26% yield, and EI mass spectrum showed a charge peak m/z= 2276.20.
5.3. Synthesis of organometallic complex (54):
referring to the synthesis method of the metal complex (7), the difference is that the intermediate (7-a) is changed to the intermediate (54-b) (1 eq,14 g), and the acetylacetone is changed to 2, 6-tetramethyl-3, 5-heptanedione. This gave a dark red metal complex (54), 6.6g, 42% yield, and EI mass spectrum showed a charge peak m/z= 1286.27.
EXAMPLE 6 Synthesis of organometallic Complex (79)
Figure BDA0003308665060000242
6.1. Synthetic intermediate (79-a):
referring to the synthesis method of the compound intermediate (5-a), the difference is that phenylboronic acid is changed into an intermediate (5-b) (1 eq,100 g), and 3-chloro-6-bromodibenzofuran is changed into 1-bromo-4-trifluoromethylisoquinoline. The solid intermediate (79-a), 81.8g, was obtained in 69% yield, and the EI mass spectrum showed a charge peak m/z= 439.12.
6.2. Synthetic intermediate (79-b):
the reference compound intermediate (5-d) was synthesized with the difference that 7, 8-benzoquinoline was changed to 2- (naphthalen-1-yl) pyridine (4.4 eq,50 g). Yellow intermediate (79-b), 14.8g, yield 45%, EI mass spectrum showing charge peaks m/z= 1272.19, was obtained.
6.3. Synthesis of organometallic complex (79):
referring to the synthesis method of the metal complex (5), the difference is that the intermediate (5-d) is changed to the intermediate (79-b) (1 eq,14 g), and the intermediate (5-c) is changed to the intermediate (79-a). This gave a dark red metal complex (79), 8.69g, yield 38%, and EI mass spectrum showed a charge peak m/z= 1039.24.
EXAMPLE 7 Synthesis of organometallic Complex (113)
Figure BDA0003308665060000243
Figure BDA0003308665060000251
7.1. Synthetic intermediate (113-a):
the synthesis method of the reference compound intermediate (5-a) is different in that phenylboronic acid is changed into 3-biphenylboronic acid (1 eq,200 g), and 3-chloro-6-bromodibenzofuran is changed into 3-bromo-4-chlorobenzoketone. This gave solid intermediate (113-a), 182.3g, 59% yield, EI mass spectrum showing charge peaks m/z= 306.08.
7.2. Synthetic intermediate (113-b):
in a dry two-necked flask, the intermediate (113-a) (1 eq,150 g) was placed, 500mL of anhydrous tetrahydrofuran was added for dissolution, then methyl magnesium bromide (2.1 eq) was added, the reaction was stirred at 50℃for 12 hours, cooled to room temperature after completion of the reaction, then dried by spin-drying, dried over dichloromethane and water, dried over magnesium sulfate, and then separated and purified by a silica gel column to give a solid intermediate (113-b), 72.6g, yield 46%, and EI mass spectrum showed a charge peak m/z= 322.11.
7.3. Synthetic intermediate (113-c):
the vacuum and filling with nitrogen were repeated three times in a dry 250mL bottle, and intermediate (113-b) (1 eq,70 g) was added with glacial acetic acid (50 mL) as solvent, followed by dropwise addition of concentrated sulfuric acid (10 eq) and heating to 80 ℃ for 2 hours. After the reaction, 1L of ice water was poured, and the precipitated solid was filtered and washed three times with water and methanol to obtain a white solid intermediate (113-c), 47.6g, yield 72%, and EI mass spectrum showed a charge peak m/z=304.10.
7.4. Synthetic intermediate (113-d):
reference is made to the process for the synthesis of compound intermediate (5-b) except that intermediate (5-a) is changed to intermediate (113-c) (1 eq,45 g). This gave solid intermediate (113-d), 41.0g, yield 70%, and EI mass spectrum showed charge peak m/z= 396.23.
7.5. Synthetic intermediate (113-e):
referring to the synthesis method of compound intermediate (5-a), the difference is that phenylboronic acid is changed to intermediate (113-d) (1 eq,40 g), and 3-chloro-6-bromodibenzofuran is changed to 1-chloroisoquinoline-6-carbonitrile. The solid intermediate (113-e), 26g, yield 61%, was obtained and the EI mass spectrum showed a charge peak m/z= 422.18.
7.6. Synthetic intermediate (113-f):
the reference compound intermediate (5-d) was synthesized with the difference that 7, 8-benzoquinoline was changed to intermediate (113-e) (4.4 eq,26 g). A reddish brown intermediate (113-f), 9.9g, 33% yield, was obtained and the EI mass spectrum showed a charge peak m/z= 2140.55.
7.7. Synthesis of organometallic complex (113):
referring to the synthesis method of the metal complex (7), the difference is that the intermediate (7-a) is changed to the intermediate (113-f) (1 eq,9.9 g), and the acetylacetone is changed to 2-picolinic acid. This gave a dark red metal complex (113), 6.5g, yield 61%, and EI mass spectrum showed a charge peak m/z= 1157.34.
Synthesis example 8 Synthesis of organometallic Complex (133)
Figure BDA0003308665060000252
8.1. Synthetic intermediate (133-a):
the synthesis method of the reference compound intermediate (5-a) is different in that 3-chloro-6-bromodibenzofuran is changed into 3-bromo-5-iodotoluene (1 eq,200 g). Solid intermediate (133-a), 129.7g, yield 78%, EI mass spectrum showing charge peaks m/z= 246.00, was obtained.
8.2. Synthetic intermediate (133-b):
reference is made to the process for the synthesis of compound intermediate (5-b) except that intermediate (5-a) is changed to intermediate (133-a) (1 eq,129.7 g). To give solid intermediate (133-b), 116.3g, 75% yield, EI mass spectrum showed charge peak m/z= 294.18.
8.3. Synthetic intermediate (133-c):
referring to the synthesis of compound intermediate (5-a), the difference is that phenylboronic acid is changed to intermediate (133-b) (1 eq,115 g), and 3-chloro-6-bromodibenzofuran is changed to 3-bromo-4-iodophenol. To give solid intermediate (133-c), 87.2g, 66% yield, EI mass spectrum showed charge peak m/z= 338.03.
8.4. Synthetic intermediate (133-d):
reference is made to a process for the synthesis of compound intermediate (113-c), except that intermediate (113-b) is changed to intermediate (133-c) (1 eq,85 g). To give solid intermediate (133-d), 61.7g, 73% yield, EI mass spectrum showed charge peak m/z= 336.01.
8.5. Synthetic intermediate (133-e):
reference is made to the process for the synthesis of compound intermediate (5-b) except that intermediate (5-a) is changed to intermediate (133-d) (1 eq,60 g). The solid intermediate (133-e), 46.0g, yield 69%, was obtained and the EI mass spectrum showed a charge peak m/z= 384.19.
8.6. Synthetic intermediate (133-f):
referring to the synthesis of compound intermediate (5-a), the difference is that phenylboronic acid is changed to intermediate (133-e) (1 eq,45 g), and 3-chloro-6-bromodibenzofuran is changed to 1-chloroisoquinoline-6-carbonitrile. This gave solid intermediate (133-f), 35.5g, 67% yield, and EI mass spectrum showed a charge peak m/z= 453.13.
8.7. Synthetic intermediate (133-g):
the reference compound intermediate (5-d) was synthesized with the difference that 7, 8-benzoquinoline was changed to 1-phenylisoquinoline (4.4 eq,50 g). A reddish brown intermediate (133-g), 31.0g, yield 44%, and EI mass spectrum showing charge peaks m/z= 1272.20, was obtained.
8.8. Synthesis of organometallic complex (133):
Referring to the synthesis method of the metal complex (5), the difference is that the intermediate (5-d) is changed to the intermediate (133-g) (1 eq,10 g), and the intermediate (5-c) is changed to the intermediate (133-f). This gave a dark red metal complex (133), 6.79g, 41% yield, and the EI mass spectrum showed a charge peak m/z= 1053.26.
EXAMPLE 9 Synthesis of organometallic Complex (146)
Figure BDA0003308665060000261
9.1. Synthetic intermediate (146-a):
the synthesis method of the reference compound intermediate (5-a) is different in that 3-chloro-6-bromodibenzofuran is changed into 4, 6-dibromodibenzofuran (1 eq,200 g). Solid intermediate (146-a), 139.2g, was obtained in 70% yield, and EI mass spectrum showed charge peak m/z=322.00.
9.2. Synthetic intermediate (146-b):
reference is made to a process for the synthesis of compound intermediate (5-b) except that intermediate (5-a) is changed to intermediate (146-a) (1 eq,139 g). This gave solid intermediate (146-b), 115.1g, yield 72%, EI mass spectrum showing charge peaks m/z= 370.17.
9.3. Synthetic intermediate (146-c):
referring to the synthesis of compound intermediate (5-a), the difference is that phenylboronic acid is changed to intermediate (146-b) (1 eq,115 g), and 3-chloro-6-bromodibenzofuran is changed to 1-chloroisoquinoline-6-carbonitrile. This gave a solid intermediate (146-c), 84.9g, yield 69%, EI mass spectrum showing charge peaks m/z= 396.13.
9.4. Synthetic intermediate (146-d):
the reference compound intermediate (5-d) was synthesized with the difference that 7, 8-benzoquinoline was changed to intermediate (146-c) (4.4 eq,80 g). This gives a reddish brown intermediate (146-d), 37.4g, 40% yield, and an EI mass spectrum showing a charge peak m/z= 2036.35.
9.5. Synthesis of organometallic complex (146):
the synthesis method of the metal complex (7) was referred to, except that the intermediate (7-a) was changed to the intermediate (146-d) (1 eq,30 g). This gave a dark red metal complex (146), 12.4g, 39% yield, EI mass spectrum showing a charge peak m/z= 1082.25.
EXAMPLE 10 Synthesis of organometallic Complex (158)
Figure BDA0003308665060000271
10.1. Synthetic intermediate (158-a):
the synthesis method of the reference compound intermediate (5-a) is different in that 3-chloro-6-bromodibenzofuran is changed into 4, 6-dibromodibenzothiophene (1 eq,200 g). Solid intermediate (158-a), 135.2g, was obtained in 68% yield, and the EI mass spectrum showed a charge peak m/z= 337.98.
10.2. Synthetic intermediate (158-b):
the synthesis method of the reference compound intermediate (5-b) is different in that the intermediate (5-a) is changed to the intermediate (158-a) (1 eq,130 g). To give solid intermediate (158-b), 106.9g, 72% yield, EI mass spectrum showed charge peak m/z= 386.15.
10.3. Synthetic intermediate (158-c):
Referring to the synthesis of compound intermediate (5-a), the difference is that phenylboronic acid is changed to intermediate (158-b) (1 eq,105 g), and 3-chloro-6-bromodibenzofuran is changed to 1-chloroisoquinoline-6-carbonitrile. Solid intermediate (158-c), 77.3g, yield 69%, EI mass spectrum showing charge peaks m/z= 412.10, was obtained.
10.4. Synthetic intermediate (158-d):
the reference compound intermediate (5-d) was synthesized with the difference that 7, 8-benzoquinoline was changed to intermediate (158-c) (4.4 eq,75 g). A reddish brown intermediate (158-d), 34.7g, 40% yield, was obtained and the EI mass spectrum showed a charge peak m/z= 2100.26.
10.5. Synthesis of organometallic complex (158):
referring to the synthesis method of the metal complex (5), the difference is that the intermediate (5-d) is changed to the intermediate (158-d) (1 eq,30 g), and the intermediate (5-c) is changed to 2-phenylbenzoxazole. This gave a dark red metal complex (158), 9.7g, yield 27%, and EI mass spectrum showed a charge peak m/z= 1253.21.
EXAMPLE 11 Synthesis of organometallic Complex (197)
Figure BDA0003308665060000272
11.1. Synthetic intermediate (197-a):
the synthesis method of the reference compound intermediate (5-a) is different in that phenylboronic acid is changed into 1-naphthalene boronic acid (1 eq,50 g), and 3-chloro-6-bromodibenzofuran is changed into 1-bromoisoquinoline. This gave a solid intermediate (197-a), 60.8g, yield 82%, EI mass spectrum showing charge peaks m/z= 255.10. 11.2. Synthesis of organometallic Complex (197):
Referring to the synthesis method of the metal complex (5), the difference is that the intermediate (5-d) is changed to the intermediate (158-d) (1 eq,30 g), and the intermediate (5-c) is changed to the intermediate (197-a). This gave a dark red metal complex (197), 16.7g, yield 46%, EI mass spectrum showing a charge peak m/z= 1269.26.
EXAMPLE 12 Synthesis of organometallic Complex (209)
Figure BDA0003308665060000281
12.1 Synthesis of intermediate (209-a):
referring to the synthesis of compound intermediate (5-a), the difference is that phenylboronic acid is changed to intermediate (5-b) (1 eq,200 g), and 3-chloro-6-bromodibenzofuran is changed to 2-chloro-5-cyanoquinoline. To give solid intermediate (209-a), 167.0g, yield 78%, EI mass spectrum shows charge peak m/z= 396.13.
12.2. Synthetic intermediate (209-b):
the reference compound intermediate (5-d) was synthesized with the difference that 7, 8-benzoquinoline was changed to 2-phenylpyridine (4.4 eq,30 g). This gives yellow intermediate (209-b), 41.0g, yield 87%, and EI mass spectrum shows charge peaks m/z= 1072.14.
12.3 Synthesis of organometallic Complex (209):
referring to the synthesis method of the metal complex (5), the difference is that the intermediate (5-d) is changed to the intermediate (209-b) (1 eq,15 g), and the intermediate (5-c) is changed to the intermediate (209-a). This gave a dark red metal complex (209), 10.3g, 41% yield, and the EI mass spectrum showed a charge peak m/z= 896.22.
EXAMPLE 13 Synthesis of organometallic Complex (240)
Figure BDA0003308665060000282
Figure BDA0003308665060000291
13.1. Synthetic intermediate (240-a):
the vacuum and filling with nitrogen were repeated three times in a dry 250mL bottle, sodium hydride (10 eq) was placed, then 1-adamantaneformate (1 eq,50 g) was added, stirred at room temperature for 40 minutes, then 1-adamantaneketone (1 eq) was slowly added, heated to 60 ℃ for reaction for 4 hours, then ice water (1000 mL) was slowly added to quench the remaining sodium hydride, then extracted with dichloromethane, concentrated to give a reddish brown liquid, and after distillation a clear liquid intermediate (240-a), 48.1g, yield 55%, and eimass spectrum showed charge peaks m/z= 339.23.
13.2. Synthetic intermediate (240-b):
in a dry 250mL bottle was placed 2,3,4, 5-tetrafluoro-6-aminobenzoic acid (1 eq,500 g), vacuum and filling with nitrogen were repeated three times, anhydrous tetrahydrofuran (100 mL) was added, then a tetrahydrofuran solution of lithium aluminum hydride (1.5 eq) was slowly dropped at 0 ℃, stirring was performed at room temperature for 4 hours after the dropping was completed, then ice water (1000 mL) was slowly added to quench the remaining lithium aluminum hydride, then extraction with dichloromethane was performed, dichloromethane was distilled off by spin, and after drying to obtain a solid intermediate (240-b), 284.6g, yield 61%, EI mass spectrum showed a charge peak m/z= 195.03.
13.3. Synthetic intermediate (240-c):
in a dry 250mL bottle was placed p-bromoacetophenone (1.1 eq), intermediate (240-b) (1 eq,280 g), ruCl 2 (PPh 3 ) 3 (0.01 eq) and potassium hydroxide (2 eq), then repeatedly vacuumizing and filling with nitrogen three times, then adding anhydrous toluene (100 mL), stirring at 120 ℃ for reaction for 24 hours, and adding dichloromethane for extraction after spin-drying the reaction solutionThe mixture was concentrated and purified by passing through a column at a ratio of petroleum ether to ethyl acetate of 12:1 to give an off-white intermediate (240-c), 407.7g, 80% yield, and EI mass spectrum showing a charge peak m/z= 354.96.
13.4. Synthetic intermediate (240-d):
the synthesis method of the reference compound intermediate (5-b) was different in that the intermediate (5-a) was changed to the intermediate (240-c) (1 eq,400 g). This gave solid intermediate (240-d), 308.9g, yield 68%, EI mass spectrum showing charge peaks m/z= 403.14.
13.5. Synthetic intermediate (240-e):
referring to the synthesis of compound intermediate (5-a), the difference is that phenylboronic acid is changed to intermediate (240-d) (1 eq,300 g), and 3-chloro-6-bromodibenzofuran is changed to 2, 6-dibromoacetophenone. This gave solid intermediate (240-e), 123.2g, yield 35%, and EI mass spectrum showed charge peak m/z= 473.00.
13.6. Synthetic intermediate (240-f):
The synthesis method of the reference compound intermediate (5-a) is different in that 3-chloro-6-bromodibenzofuran is changed into an intermediate (240-e) (1 eq,123 g). This gave solid intermediate (240-f), 96.8g, yield 79%, EI mass spectrum showing charge peaks m/z= 471.12.
13.7 Synthesis of intermediate (240-g):
the synthesis method of the compound intermediate (113-b) was referred to, except that the intermediate (113-a) was changed to the intermediate (240-f) (1 eq,96.8 g). The solid intermediate (240-g), 80.1g, was obtained in 80% yield, and the EI mass spectrum showed a charge peak m/z= 487.16.
13.8. Synthetic intermediate (240-h):
the synthesis method of the compound intermediate (113-c) was referred to, except that the intermediate (113-b) was changed to the intermediate (240-g) (1 eq,80 g). The solid intermediate (240-h), 27.7g, yield 36%, was obtained and the EI mass spectrum showed a charge peak m/z= 469.15.
13.9. Synthetic intermediate (240-i):
reference is made to the process for the synthesis of compound intermediate (5-d) except that 7, 8-benzoquinoline is changed to intermediate (240-h) (4.4 eq,27.7 g). Yellow intermediate (240-i), 5.3g, 17% yield, EI mass spectrum showing charge peaks m/z= 2328.43, was obtained.
13.10. Synthesis of organometallic complex (240):
referring to the synthesis method of the metal complex (7), the difference is that the intermediate (7-a) is changed to the intermediate (240-i) (1 eq,5.3 g), and the acetylacetone is changed to the intermediate (240-a). This gave a dark red metal complex (240), 2.1g, 31% yield, and the EI mass spectrum showed a charge peak m/z= 1468.48.
EXAMPLE 14 Synthesis of organometallic Complex (268)
Figure BDA0003308665060000301
14.1. Synthetic intermediate (268-a):
the synthesis method of the reference compound intermediate (5-a) is different in that 3-chloro-6-bromodibenzofuran is changed into 2-chloro-6-bromodibenzothiophene (1 eq,200 g). Solid intermediate (268-a), 149.0g, yield 75%, EI mass spectrum showing charge peaks m/z= 294.03, was obtained.
14.2. Synthetic intermediate (268-b):
the synthesis method of the reference compound intermediate (5-b) is different in that the intermediate (5-a) is changed to an intermediate (268-a) (1 eq,149 g). Solid intermediate (268-b), 150.7g, yield 77%, EI mass spectrum showing charge peaks m/z= 386.15, was obtained.
14.3. Synthetic intermediate (268-c):
referring to the synthesis of compound intermediate (5-a), the difference is that phenylboronic acid is changed to intermediate (268-b) (1 eq,150 g), and 3-chloro-6-bromodibenzofuran is changed to 2-bromo-5-fluoroquinoline. This gave solid intermediate (268-c), 72.4g, yield 46%, EI mass spectrum showing charge peaks m/z= 405.10.
14.4. Synthetic intermediate (268-d):
the synthesis method of the reference compound intermediate (5-d) was different in that 7, 8-benzoquinoline was changed to intermediate (268-c) (4.4 eq,70 g). A reddish brown intermediate (268-d), 26.9g, yield 33%, and EI mass spectrum showing charge peaks m/z= 2072.24, was obtained.
14.5. Synthesis of organometallic complex (268):
referring to the synthesis method of the metal complex (5), the difference is that the intermediate (5-d) is changed to the intermediate (268-d) (1 eq,20 g), and the intermediate (5-c) is changed to 2-phenylpyridine. This gave a dark red metal complex (268), 13.2g, 59% yield, and an EI mass spectrum showing a charge peak m/z= 1155.22.
EXAMPLE 15 Synthesis of organometallic Complex (293)
Figure BDA0003308665060000302
15.1. Synthetic intermediate (293-a):
referring to the synthesis of compound intermediate (5-a), the difference is that phenylboronic acid is changed to intermediate (268-b) (1 eq,150 g), and 3-chloro-6-bromodibenzofuran is changed to 2-bromo-5, 6-bis (trifluoromethyl) quinoline. This gave solid intermediate (293-a), 68.9g, yield 35%, and EI mass spectrum showed charge peaks m/z= 507.11.
15.2. Synthetic intermediate (293-b):
referring to the synthesis of compound intermediate (5-d), the difference was that 7, 8-benzoquinoline was changed to intermediate (293-a) (4.4 eq,68.9 g). This gives a reddish brown intermediate (293-b), 34.5g, 45% yield, and an EI mass spectrum showing a charge peak m/z= 2480.27.
15.3. Synthesis of organometallic complex (293):
referring to the synthesis method of the metal complex (5), the difference is that the intermediate (5-d) is changed to the intermediate (293-b) (1 eq,30 g), and the intermediate (5-c) is changed to 3-phenylisoquinoline. This gave a dark red metal complex (293), 11.6g, 34% yield, and an EI mass spectrum showing a charge peak m/z= 1409.25.
EXAMPLE 16 Synthesis of organometallic Complex (327)
Figure BDA0003308665060000311
16.1. Synthetic intermediate (327-a):
referring to the synthesis of compound intermediate (5-a), the difference is that phenylboronic acid is changed to intermediate (158-b) (1 eq,50 g), and 3-chloro-6-bromodibenzofuran is changed to 2-bromo-5-trifluoromethylquinoline. Solid intermediate (327-a), 16.5g, was obtained in 28% yield, and EI mass spectrum showed charge peak m/z= 455.10.
16.2. Synthesis of organometallic complex (327):
referring to the synthesis method of the metal complex (5), the difference is that the intermediate (5-d) is changed to the intermediate (209-b) (1 eq,15 g), and the intermediate (5-c) is changed to the intermediate (327-a). This gave a dark red metal complex (327), 12.6g, yield 47%, EI mass spectrum showing charge peaks m/z= 956.19.
EXAMPLE 17 Synthesis of organometallic Complex (343)
Figure BDA0003308665060000312
17.1. Synthetic intermediate (343-a):
referring to the synthesis of compound intermediate (5-a), the difference is that phenylboronic acid is changed to intermediate (146-b) (1 eq,50 g), and 3-chloro-6-bromodibenzofuran is changed to 2-bromo-6-cyanoquinoline. This gave solid intermediate (343-a), 25.7g, yield 48%, and EI mass spectrum showed charge peak m/z= 396.13.
17.2. Synthesis of organometallic complex (343):
referring to the synthesis method of the metal complex (5), the difference is that the intermediate (5-c) is changed to the intermediate (343-a) (1 eq,12.5 g). This gave a dark red metal complex (343), 15.2g, yield 51%, and EI mass spectrum showed a charge peak m/z= 944.22.
EXAMPLE 18 Synthesis of organometallic Complex (352)
Figure BDA0003308665060000321
18.1. Synthetic intermediate (352-a):
in a dry two-necked flask was placed pinacol biborate (3 eq), 2, 6-dibromophenol (1 eq,300 g), pd (dppf) 2 Cl 2 (0.2 eq) and potassium acetate (6 eq) were added, then 250mL of a mixed solution of dioxane and water in a ratio of 3:1 was added, and the mixture was stirred at 90℃for reaction for 12 hoursCooling to room temperature, spin-drying after the reaction, drying with dichloromethane and water solution, spin-drying again after drying with magnesium sulfate, and separating and purifying with silica gel chromatographic column. Solid intermediate (352-a), 291.0g, 70% yield, was obtained and the EI mass spectrum showed a charge peak m/z= 346.21.
18.2. Synthetic intermediate (352-b):
referring to the synthesis of compound intermediate (5-a), the difference is that phenylboronic acid is changed to intermediate (352-a) (1 eq,300 g), and 3-chloro-6-bromodibenzofuran is changed to 2-bromo-4-phenylpyridine. Solid intermediate (352-b), 181.9g, yield 58%, EI mass spectrum showing charge peak m/z= 373.18 was obtained.
18.3. Synthetic intermediate (352-c):
referring to the synthesis of compound intermediate (5-a), the difference is that phenylboronic acid is changed to intermediate (352-b) (1 eq,181.9 g), and 3-chloro-6-bromodibenzofuran is changed to 2-bromo-5, 6-bis (trifluoromethyl) quinoline. Solid intermediate (352-c), 129.3g, yield 52%, EI mass spectrum showing charge peaks m/z= 510.12, was obtained.
18.4. Synthetic intermediate (352-d):
reference was made to the method for synthesizing compound intermediate (113-c) except that intermediate (113-b) was changed to intermediate (352-c) (1 eq,129.3 g). This gave solid intermediate (352-d), 46.4g, 36% yield, EI mass spectrum showing charge peaks m/z= 508.10.
18.5. Synthetic intermediate (352-e):
referring to the synthesis of compound intermediate (5-d), the difference was that 7, 8-benzoquinoline was changed to intermediate (352-d) (4.4 eq,46.4 g). This gave a reddish brown intermediate (352-e), 21.1g, 41% yield, and EI mass spectrum showed a charge peak m/z= 2484.25.
18.6. Synthesis of organometallic complex (352):
the synthesis method of the metal complex (7) was referred to, except that the intermediate (7-a) was changed to the intermediate (352-e) (1 eq,20 g). This gave a dark red metal complex (352), 6.5g, 31% yield, and EI mass spectrum showed a charge peak m/z= 1306.20.
1.2 calculation of transition metal Complex energy level data
The molecular geometry is optimized by using TD-DFT (time-Density functional theory) through Gaussian 09W (Gaussian Inc.), first using a Semi-empirical method "group State/Semi-empirical/Default Spin/AM1" (Charge 0/Spin single), and then the energy structure of the organic molecule is calculated by TD-DFT (time-Density functional theory) method as "TD-SCF/DFT/Default Spin/B3PW91" and the basis set "6-31G (d)" (Charge 0/Spin single). The HOMO and LUMO energy levels are calculated according to the following calibration formula, and S1, T1 and resonance factor f (S1) are directly used.
HOMO(eV)＝((HOMO(G)×27.212)-0.9899)/1.1206；
LUMO(eV)＝((LUMO(G)×27.212)-2.0041)/1.385。
HOMO, LUMO, T1 and S1 are direct calculations of Gaussian 09W in Hartree. The results are shown in Table 1 below. The energy level data of each transition metal complex is shown in Table 1, wherein HOMO represents the highest occupied molecular orbital (Highest Occupied Molecular Orbital), LUMO represents the lowest unoccupied molecular orbital (Lowest Unoccupied Molecular Orbital), S 1 Represents the lowest singlet energy level, T 1 Representing triplet energy levels.
TABLE 1 energy level data for transition metal complexes
Figure BDA0003308665060000322
/>
Figure BDA0003308665060000331
The structures of REF1 and REF2 are as follows:
Figure BDA0003308665060000332
1.3 preparation and characterization of OLED devices
OLED device structure
The structure of the device is as follows: ITO/HIL
Figure BDA0003308665060000334
/HTL/>
Figure BDA0003308665060000335
/EBM/>
Figure BDA0003308665060000336
/EML/>
Figure BDA0003308665060000337
/ETL/>
Figure BDA0003308665060000338
A cathode.
Wherein the EML consists of H-Host, E-Host and transition metal complex, wherein the mass ratio of the H-Host to the E-Host is 6:4, and the doping amount of the transition metal complex is 10% (w/w) of the total mass of the H-Host and the E-Host. The light emitting layer guest material uses the transition metal complex (5) or (7) or (17) or (54) or (79) or (113) or (133) or (146) or (158) or (197) or (209) or (240) or (268) or (293) or (327) or (343) or (352) or REF1 or REF 2) of the embodiment of the present invention. ETL consists of LiQ (8-hydroxyquinoline-lithium) doped with 40% (w/w) ETM.
The OLED device used the following material structure:
Figure BDA0003308665060000333
/>
Preparation of OLED device
a. Cleaning the conductive glass substrate, namely cleaning the conductive glass substrate by using various solvents, such as chloroform, ketone and isopropanol, and then performing ultraviolet ozone plasma treatment; the following cleaning methods are specifically adopted in this embodiment: rinsed and immersed in ultrasonic vibration for 5 minutes and then air-dried.
b、
Figure BDA0003308665060000341
In high vacuum (1X 10) -6 Mbar, mbar).
c. The cathode was thermally evaporated in a high vacuum (1X 10-6 mbar) from LiF/Al (1 nm/150 nm).
d. Encapsulation the device was encapsulated with an ultraviolet curable resin in a nitrogen glove box.
Characterization of OLED devices
The current-voltage-luminance (JVL) characteristics of the OLED devices 1 to 17 were characterized by a characterization apparatus while recording important parameters such as emission peak wavelength, external quantum efficiency and device lifetime. The relative parameters of the OLED device are shown in table 4:
TABLE 4 relative data for devices made with different dopants
Figure BDA0003308665060000342
As can be seen from the data in Table 4, the external quantum efficiency and the device lifetime of the OLED device are both significantly improved by using the metal complex material of the present invention as the doping material for the EML (light emitting layer) compared with the devices made of the REF1 and REF2 metal complexes, and the wavelength of the light emitting wave of the device is larger than that of the comparative examples (REF 1 and REF 2), i.e., the light color is red shifted.
The reason for this benefit is inferred to be that the metal complex provided by the present invention contains at least one-CN, -F or-CF in its structure 3 And the electron withdrawing groups are substituted, and the electron withdrawing groups can help electron transmission in the device, so that electrons can be effectively used, the luminous efficiency of the device is improved, the starting voltage is reduced, and the service life of the device is prolonged. In addition, electron-withdrawing groups are substituted, so that the LUMO energy level of the metal complex can be greatly stabilized, meanwhile, the conjugated system of the metal complex can be increased due to the fact that the hetero atom system contains the defined phenyl groups, and the two groups are matched to enable the luminescence of the metal complex to be greatly red-shifted, so that high-efficiency deep red light color is realized.
If the invention is further optimized, such as optimizing the structure of the device and optimizing the combination of the HTM, the ETM and the main material, the performance, particularly the efficiency, the driving voltage and the service life of the device are further improved.
The technical features of the above-described embodiments and examples may be combined in any suitable manner, and for brevity of description, all of the possible combinations of the technical features of the above-described embodiments and examples are not described, however, as long as there is no contradiction between the combinations of the technical features, they should be considered to be within the scope described in the present specification. The above examples merely represent a few embodiments of the present invention and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Further, it is understood that various changes and modifications of the present invention may be made by those skilled in the art after reading the above teachings, and equivalents thereof are intended to fall within the scope of the present invention. It should also be understood that, based on the technical solutions provided by the present invention, those skilled in the art obtain technical solutions through logical analysis, reasoning or limited experiments, all of which are within the scope of protection of the appended claims. The scope of the invention should, therefore, be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled.

Claims (12)

1. A metal complex has a structure shown in a formula (I) or a formula (II):
Figure FDA0003308665050000011
wherein,,
l is selected from monovalent anionic organic ligands;
m is selected from 1 or 2 or 3;
X 1 ，X 2 ，X 3 each occurrence is independently selected from CR 1 Or N;
X 4 ，X 5 ，X 6 ，X 7 ，X 8 ，X 9 each occurrence is independently selected from CR 2 Or N;
y is independently selected from CR for each occurrence 3 R 4 ，NR 3 O, S or SO 2 ；
R 1 ，R 2 ，R 3 ，R 4 Each occurrence is independently selected from: -H, -D, linear alkyl having 1 to 20C atoms, linear alkoxy having 1 to 20C atoms, linear thioalkoxy having 1 to 20C atoms, branched alkyl having 3 to 20C atoms, cyclic alkyl having 3 to 20C atoms, branched alkoxy having 3 to 20C atoms, or cyclic alkoxy having 3 to 20C atoms, branched thioalkoxy having 3 to 20C atoms, or cyclic thioalkoxy having 3 to 20C atoms, silyl, keto having 1 to 20C atoms, alkoxycarbonyl having 2 to 20C atoms, aryloxycarbonyl having 7 to 20C atoms, -CN, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, -CF 3 -Cl, -Br, -F, an aromatic group having 6 to 60 ring atoms substituted or unsubstituted, a heteroaromatic group having 5 to 60 ring atoms substituted or unsubstituted, an aryloxy group having 6 to 60 ring atoms substituted or unsubstituted, a heteroaryloxy group having 5 to 60 ring atoms substituted or unsubstituted, or a combination of these groups; adjacent R 1 Or adjacent R 2 With or without each other being cyclic;
at least one R 2 Selected from-CN, -F or-CF 3 。
2. The metal complex according to claim 1, wherein the metal complex is selected from any one of structures represented by formulas (1-1) to (1-6):
Figure FDA0003308665050000012
3. the metal complex of claim 1 or 2, wherein X is 7 Selected from CR 2 And R is 2 Selected from-CN, -F or-CF 3 。
4. The metal complex according to claim 1 or 2, wherein,
Figure FDA0003308665050000021
a group selected from any one of the following:
Figure FDA0003308665050000022
and/or
Figure FDA0003308665050000023
A group selected from any one of the following: />
Figure FDA0003308665050000024
Wherein: * Representing the ligation site.
5. The metal complex according to claim 1 or 2, wherein,
Figure FDA0003308665050000025
each independently selected from any one of the following groups:
Figure FDA0003308665050000031
/>
wherein: * Representing the ligation site.
6. The metal complex of claim 1, wherein L is selected from the following structural formulas:
Figure FDA0003308665050000032
wherein,,
Ar 1 、Ar 2 、Ar 3 each independently selected from a substituted or unsubstituted aromatic group having 5 to 30 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms, or a substituted or unsubstituted non-aromatic ring system having 5 to 30 ring atoms;
R 5 、R 6 、R 7 each occurrence is independently selected from: -H, -D, linear alkyl having 1 to 20C atoms, linear alkoxy having 1 to 20C atoms, linear thioalkoxy having 1 to 20C atoms, branched alkyl having 3 to 20C atoms, cyclic alkyl having 3 to 20C atoms, branched alkoxy having 3 to 20C atoms, cyclic alkoxy having 3 to 20C atoms, branched thioalkoxy having 3 to 20C atoms, cyclic thioalkoxy having 3 to 20C atoms, silyl, keto having 1 to 20C atoms, alkoxycarbonyl having 2 to 20C atoms, aryloxycarbonyl having 7 to 20C atoms, -CN, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, -CF 3 -Cl, -Br, -F, an aromatic group having 6 to 60 ring atoms substituted or unsubstituted, a heteroaromatic group having 5 to 60 ring atoms substituted or unsubstituted, an aryloxy group having 6 to 60 ring atoms substituted or unsubstituted, a heteroaryloxy group having 5 to 60 ring atoms substituted or unsubstituted, or a suitable combination of the foregoing;
* Represents the site of attachment to Ir.
7. The metal complex of claim 6, wherein Ar 1 、Ar 2 、Ar 3 Each independently selected from the following groups:
Figure FDA0003308665050000041
wherein,,
v each time go outNow, independently selected from C, CR 8 Or N;
w is independently selected from CR for each occurrence 9 R 10 ，NR 9 ，O，S，N，PR 9 ，BR 9 Or SiR 9 R 10 ；
R 8 、R 9 、R 10 Each occurrence is independently selected from: -H, -D, linear alkyl having 1 to 20C atoms, linear alkoxy having 1 to 20C atoms, linear thioalkoxy having 1 to 20C atoms, branched alkyl having 3 to 20C atoms, or cyclic alkyl having 3 to 20C atoms, branched alkoxy having 3 to 20C atoms, or cyclic alkoxy having 3 to 20C atoms, branched thioalkoxy having 3 to 20C atoms, or cyclic thioalkoxy having 3 to 20C atoms, silyl, keto having 1 to 20C atoms, alkoxycarbonyl having 2 to 20C atoms, aryloxycarbonyl having 7 to 20C atoms, -CN, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, -CF 3 -Cl, -Br, -F, a substituted or unsubstituted alkenyl group having 2 to 20C atoms, a substituted or unsubstituted aryl group having 6 to 60 ring atoms, a substituted or unsubstituted heteroaryl group having 5 to 60 ring atoms, a substituted or unsubstituted aryloxy group having 6 to 60 ring atoms, a substituted or unsubstituted heteroaryloxy group having 5 to 60 ring atoms, or a combination of the foregoing; adjacent R 8 And/or R 9 With or without each other.
8. The metal complex of claim 7, wherein L is preferably selected from any one of structures (G-1) to (G-28):
Figure FDA0003308665050000042
wherein one Q in the ligand is selected from C, and the other Q is selected from N.
9. The metal complex according to claim 8, which is selected from any one of the formulas (2-1) to (2-16):
Figure FDA0003308665050000051
10. a mixture comprising the metal complex according to any one of claims 1 to 9 and at least one organic functional material, wherein the organic functional material is selected from at least one of a hole injecting material, a hole transporting material, an electron injecting material, an electron blocking material, a hole blocking material, a light emitting material, a host material, and an organic dye.
11. A composition comprising the metal complex of any one of claims 1 to 9 or the mixture of claim 10, and at least one organic solvent.
12. An organic electronic device comprising the metal complex of any one of claims 1 to 9 or the mixture of claim 10 or prepared from the composition of claim 11.
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